Method for producing nitrogen compounds.



C. E. ACKER.

METHOD FOR PROOUCING NHROGEN COMPOUNDS.

APPLICATION HLED SEPT. 2, 1910.

Patented Nov. 16, 1915.

2 SHEETS-SHEET 1.

MOOOM.

C. E. ACKER.

METHOD FOR PRODUCING NITROGEN COMPOUNDS.

APPLICATION FILED SEPT. 2. IBIO.

latented Nov. 16, 1915.

2 SHEETS-SHEET 2.

mmm..

tu i

LIIULII.

pounds, of which the following is a f\1lll clear, and exact escription.

`rIhis invention relates to a process for the manufacture of alkalimetal cyanids, cyanav mids and the like, and more particularly tocertain improvements in the processes de scribed in my United Statesapplications,- Serial No. 485,344, filed March 23, 1909, and Serial No.579,763, filed August 30, v19101. The processes therein disclosedconsist in initially 4reacting on a particularly reactive metal such asbarium, lithium, strontium, manganese, etc., with carbon or a carbonaacarbid of such metal, e. g., barium carbid; in then treating this carbidwith nitrogen or a nitrogenous reagent, for the purpose'of producing thecyanidV of such metal, and in nnally reacting on the barium cyanid orthe like with an alkali metal e. g., sodium, with the consequentproduction of sodium cyanid -and metallic barium. In the firstapplication, the reactions involved occur within the body or mass of amolten alloy, such alloy preferably comprising the alkali metal, the

reactive metal and a vrelatively inactive diluent metal; while in thesecond case thel reactions resulting in the formation of carbid wereconfirmed principally to the surface of the alloy, the subsequentreaction of the carbid so formed with a nitrogenous reagent occurring inthe body of a mass of sup'erposed fused salt. As I stated in the secondof the applications aforesaid, the formation of the final product wasexpedited and the process made more eficient by bringing about thereaction between the carbon and nitrogen compounds entirely outside ofthe body of alloy, and I have sincefound that a still greater increasein efficiency may be obtained by causing4 all of the reactions to occurin the body of fused salt. This application therefore relates to aprocess of this descrition, and covers the feature of electro# lytic yboth thu reactiva etal Specification of Letters Patent.

- contact with the liberated metals.

reactive metal c anid, e.

be similarly' decom` ceous reagent for the purpose of producingposed bymetallic sodium. As stated in the t. ns is. acaror ossrn'rna, NEW Yo,ass'ron'o o irnnnrrnoenn coa a conronafrron or row: y s

It THOD FOB. PRODUCING NITOGEN COO'UNDS.

ratentoa not. ic, rara;

Application med September 2, 1910. Serial No. M1190.

and the alkali metal on a suitable cathodel from the molten alloy, usinga suitable electrolyte, such for example, as sodium cyanid; and 1nlntroducing nitrogenous and carbonaceous reagents into the electrolytein such manner that the same may come directly into As stated 1napplicatlon 485,344, some portion of the reactive metal e. g., barium,might combine directly with nitrogen to' forml barium 'nitrid whichwould then react with carbonv to form barium cyanld; and that thiscyanid would in turn be decomposed bvsodium as above, with formation ofsodium cyanidand metallic barium. I stated, furthermore, that 'I bothcarbid and nitrid might be formed -under the conditions of theprocesses,and

that they might then react together to form g., vbarium cyanid, which'wou/l second application, by far the greater part of the initialformation of reactive metal carbid, e.' g., barium carbid, 1n what seemsto be a particularly favorable physical con.

dition for the absorption of nitrogen at a low temperature; and that acomparatively small proportion' of the final product is obtained as aresult of the initial formation of reactive metal 7 nitrid whichafterward combines with carbon. etc.

The chemical reactions involved in the present case,l when suicient freecarbon is present, are substantially similar to those described in myapplications above referred to, and may be represented as follows:

.It will be observed by considering reac-' tions No. 1 toNo.4representing the principal steps of the process) that the reactivemetal, e.' g., barium, passes from the nie` tellin ttate to carbid,carbid to cyanld, and

As stated inv my other applications the..

reactive metal` e. g., barium, and the alkali metal, e. g., sodium, mayeach be employed in the pure state, in the form of an alloy with eachother, or in the form of an alloy with certain heavy and relativelyinert metals such as lead, tin, etc.; the nitrogen may be employed inthe form of pure or diluted gas, ammonia, or other nitrogenous reagent;and the carbon may be employed in the form of finely divided, granular,or lump charcoal, coal, coke, hydrocarbon gas, fuel oil, lamp black, acyanid, cyanamid or other carbonaceous reagent. By the term carbonaceousreagent as used in the appended claims, I mean therefore, carbon or anycompound thereof capable of yielding carbon under the conditions vof theprocess; While the term nitrogenous reagent correspondingly refers toand includes nitrogen or any compound including nitrogen as aningredient thereof, which will yield that element under such conditions.

If the source of carbon is a gas, fuel oil, or lamp black, the resultantcarbid, produced by the combination of the reactive metal .with carbon(as pointed out in application No. 485,844) is found to be present infinely divided form.

As stated in application 579,7 63 filed August 30, 1910, the carbidproduced in the process, is in peculiarly favorable physical conditionfor the absorption of nitrogen, being apparently amorphous andimpalpable and quite unlike the ordinary hard, iridescent, impurecommercial crystalline carbids known to commerce. The former is producedat a very low temperature {generally below 900o C.) and under radicallydifferent conditions from the later, which is produced in electricsmelting furnaces at a very high temperature,generally overl When bothbarium and sodium are alloyed with a heavy metal such as lead, and soutilized in the process,v-some of the reactions in which barium, sodium,carbon, etc., are concerned must obviously take place in the actualpresence of the alloy-either at the surface thereof or in contact withsome -(reaction #3) must come into actual con-l tact with sodium ascontained in the alloy. In my latter application, also, I calledattention to the fact that the presence of a considerable. body ofmolten sodium cyanid on the surface of the alloyl was an advantage. inthat the barium carbid became suspended, diffused, orv dissolved in the:cyanid and could there be more advantageously reacted upon by thenitrogenous reagent, the product ofthe reaction bein barium cyanid,which fusedreadily anldissolved in the sodium cyanid and thus came intocontact with the metallic sodium contained in the alloy, at thesurfacethereof, whereby the barium in the barium cyanid was set free atthe sur-face of the alloy, and sodium cyanid was formed; `and furtherthat the metallic barium thus liberated at the surface of thealloypromptly combined with carbon to form more carbid, which thenbecame disseminated throughout the molten cyanid as before.

' When metallic barium is liberated at the surface of the alloy, it mayrenter the alloy, if only momentarily, and then afterward combine withcarbon in contact with the surface of the alloy at4 that particularpoint to form barium carbid; at any -rate the decomposition of thebarium cyanid is effected by the sodium at the surface of the alloy, andnot elsewhere inthe mass of molten cyanid. It thus transpires that someof the intermediate reactions of the lprocess as carried out in theapparatus described in application Serial No. 579,763 .take place at thesurface of the alloy only and that they are effected by certain metalsWhile diluted with other metals, and which are therefore to some extentless effective in bringing about such reactions than they would be if inthe pure state, and not diluted, so to speak, with yother relativelyinert metals.

Il have found it desirable in carrying out these reactions at thesurface of the alloy to have a comparatively high percentage of bothreactive metal and alkali metal present in the alloy, so that they willnot be unduly diluted in which case the process proceeds smoothly andrapidly,-but I have also found that it is possible and convenient toliberate from the alloy-and within the mass -of the molten cyaniditself-both reactive metal and alkali metal in the pure state, that isto say, not in the least diluted with an inert metal such as lead,(although the two metals actually concerned in the reactions, e. g.,barium and sodium, when simultaneously liberated in the interior of themolten cyanid maybe momentarily alloyed with each other) by passing acurrent of electricity from the surface of the molten alloy constitutingan anode, through the molten lcyanid constituting an electrolyte, to asolid carbon, iron or other metal disk or grid, partly submerged in thecyanid, and constituting the cathode of an electrolytic cell. Themetallic barium thus' liberated Within the mass of the molten cyanid `instantly combines with carbon-either vthe carbon of the cathode, if thecathode ,be `of carbon, freecarbon disseminated throughout nieolai'iitself-the latter according to the following equation llr employing asolid iron or metal catli ode, as l prefer, and in case there is no freecarbon disseminated or didused throughout the molten cyanid, the abovereaction (#5) will always take place when bariumis the reactive metalused. x

llllhe same reaction will take place when lithium, or some otherreactive metal is employed instead of barium. 'Jlhe products oit thereduction of the sodiumcyanid are thus, sodium cyanamid (dialkalicyanamiol) and barium carbid, and if no freecarbon is present orafterward supplied, the reduction of the cyanid to cyan mid will proceeduntil the entire mass of cyaanid is converted into cyanamid, and theprocess may be used accordingly for the production of alkali cyanamids.When, however, free carbon is present in the molten mass at the time thebarium is liberated in a free state, or whenever it is afterwardsupplied, the c anamid which is probably always formed within the moltenmass is quickly reconverted intocyanid. When metallic barium, or otherreactive metal is set free at the surface of fthe solid cathode, andwithin the mass of molten sodiumcyanid it probably does not preserve itsmetallic character for more than a brief moment, but combines withcarbon practi-y cally at the moment of its liberation.

lI regard it as likely, in view of the 'fact that barium does reducemolten sodium cyanid to sodium cyanamid by combining with some of itscombined carbon, and in view ofv the fact that molten sodium cyanid isin intimate and close contact with the barium at the moment of itsliberatiom-pressed against it in fact by the weight of the supernatantfluid cyanid, and in view of the impalpable and amorphous character ofthe barium carbid produced in the process at so low a temperature (below900 C.) that the greater part of the barium carbid, which is concernedin the synthesis of sodium cyanid by this process is produced by bariumcombining with one element of carbon in the cyanid itself,-it beingunderstood, of course, that but a very small proportion of the wholemass of cyanid would be thus momentarily reduced--and that the freecarbon ioating around therein quickly recouverts the reduced portionback to cyanid.

The barium carbid, produced in accordance with reaction #l or reaction#5, remains suspended in the molten cyanid by reason of the agitation ofthe molten mass.

rl`he entire mass of cvanid is practically saturated with im alpablecarbid, and if a sample ot the me ten cyanid taken during? this processis moist'ene'd with water, the presence of carbid is very'evident fromthe odor of the evolved. acetylene,-although no lumps or crystals ofcarbid may be visible. The carbid 1s present in a very fine stae ofdivision.' (Some carbid may also possibly be 1n .actual solution.) Whenthe cyanid is examined under the microscope the npure colorless crystalsof cyanid loom up very large and clear, and squeezed in between thecrystals is the dark gray or black carbid apparently in the form of afilm. The moisture 1n the air attacks this film of carbid between thecrystals at the exposed edges of the film and minute bubbles of gas areconstantly given oil all along the exposed edges. E videntlythe carbidis in very soft condition since it is squeezed into the thin spacesbetween the crystals of the cvanid iii the manner described; but it isimpossible to examine it directly in the open air on account of theminute bubbles of gas which instantly cover its surface.

The specific gravity of barium carbid is4 con s1derably greater thanthat of molten sodium cvanid, but owing to the fact that the carbid. isapparently in amorphous condition, a little agitation suflices tomaintain 1t in suspension. y

he gaseous nitrogen or ammonia, or a little fuel oil, inJec'ted into thealloy, or into the molten cyanid, and used primarily as a source ofcarbon, produces all the agitationV required to maintain both the carbonand amorphous carbid in suspension in the molten cyanid. Meanwhile,nitrogen or ammonia 1s continuously or intermittently introduced intothe mass of molten cyanid in such manner as to come into contact withthe suspended carbid with which it then combines to form barium cyanid,which v fuses easily, and being perfectly miscible with the sodiumcyanid, diffuses throughout the entire molten mass. Barium cyanid isthus constantly present throughout the moltenelectrolyte and at the verysurface of the solid cathode where metallic sodium is liberated. It maybe liberated simultaneously with the barium. -As soon as pure sodium isliberated at the cathode it enters into reconsiderabh7 greater thanthat'of the molten electrolyte it cannot settle through the electrolytewithout comingr in contact with carbon, either free or combined, anduniting therewith to form barium carbid. It thus transpires that as longas there is any barium cyanid in the meltfunder normal workin@conditions it alioiild always be' present until the charge is to beinished-the liberfree at the solid cathode and therefore does notaccumulate as such within nor on the surface of the melt. If theresidual lead alloy should contain a suflicient percentage of sodium toreact with barium cyanid in the electrolyte, then such al'loyed sodiumwhen reacting With barium cyanid at the surface of the alloy, willliberate the barium' at the surface of the alloy, and it may thencombine in whole or in part with the heavy, inert metal of the alloy;but by far the greater part of the final product will bc produced as aresult of intermediate and nal reactions taking place within the mass ofthe molten cyanid at the surface of the solid cathode, or in thevicinity thereof.

The present process may be conducted in a double `compartmentelectrolytic furnace similar to the sodium furnace described inapplication Serial No. 575,189, tiled August 5, 1910, except that thesolid cathode has a hole in its shank for introducing nitrogen (and fueloil, if desired), and that the iron cover is preferably fitted with ahopper.

Referring therefore to the accompanying drawings, which illustrate oneform of apparatus which may be used: Figure 1 is a vertical crosssection of an apparatus adapted for the carrying out of my improvedprocess taken on the line I-I. Fig. 2 is a horizontal section throughthe said apparatus taken on the line II--II of Fig. 1. Fig. 3 is atransverse vertical section of said apparatus taken on the lineIII-IIIof Fig. 2. Fig. 4 is a fragmentary section taken on line IV-IV ofFig. 3.

Like parts are designated by the same reference sign throughout therespective views.

Referring now to the drawings, the furnace or inner container 1 shouldpreferably be made of cast iron or cast steel,'and the inner walls ofsuch chamber should preferably be lined with refractory material 2, suchas alumina or magnesia. The furnace casting is inclosed at the bottomand on all sides by heat insulating material 3, preferably brick or thelike. The furnace comprises two principal chambers, a primaryelectrolytic chamber 4 and a secondary chamber 5, these chambers beingseparated by a septum or wall 6, the bottom flanges 7' of which serve tosupport the adjacent side lining 2. A set of anodes 8 extend into theprimary chamber and are preferably made of some form of carbon. Theprimary chamber 4 is covered with a slab 9 of refractory material; andthe gases liberated at the anodes are conducted away through fiues 10 AThe secondary chamber 5 it fitted with a spout 11 for conducting off thefinal product, such compartment having a cover 12 spaced from thecontainer b y an an: tight gasket to prevent the admission of air intothe reaction chamber. An iron, nickel or carbon electrode 13 yprojectsthrough the cover into the mass of electrolyte 14 disl posed in thesecondary.chamber; the electro- 'the alloy may be effected eitherintermittently or continuously by mechanicalmeans or otherwise; acentrifugal pump 17 being shown in the drawings; and suitable means,such as a hopper 18, .may be provided for permitting the continuous orintermittent introduction of the salt'required in the electrolyticchamber. The secondary cathode 13 is adjustable in the air tight cover12 and has a hole extending through its shank, the upper part of whichis fitted with a valved pipe 19 for introducing nitrogen or ammonia intothe molten mass in the reaction chamber; and is also fitted with an oilfeed device 20, through which fuel oil or other hydrocarbon may beintroduced in carefully regulated quantities into the reactive chamber.An auxiliary supply pipe 21 extends through the side of the reactionchamber; its lower end being below the surface of the alloy, and suchpipe may be used to introduce nitrogen or hydrocarbon, or both, directlyinto the mass of molten metal, when desired, thus affording a means ofpreheating the nitrogen when desired. The cover 12 is also fitted with aspecially constructed hopper 22, which has an air ti ht cover and is soarranged that it may be lled with charcoal and then subjected tothe'action of a vacuum pump for the purpose of exhausting the air fromthe hopper and the charcoal contained therein, before it is charged intothe reaction chamber.

The molten cyanid is produced in the secondary chamber and normallyrises to the level of the outlet before it is permitted to run offthrough spout 11; this spout may be temporarily closed, however, topermit the cyanid to accumulate in the chamber to a much greater depth,before being tapped off.

The primary electrolyte may consist largely, at the beginning of theoperation, of molten barium chlorid-with a small proportion of sodiumchlorid.

The electrolyte in the secondary chamber consists preferably of puremolten sodium cyanid, (although it may contain any proportion of purebarium carbid, cyanid, or other barium salt from which barium may be setfree by sodium at the temperature of the operation). Both electrolytesrest on the surface of the molten lead in their rethe surface ofthe'lead land turned on.

s ectivecompartmenta. 4 rllhe anodesv vSand t e cathode 13 arethenraised slightly- .ebiqw I theicurrentis The current densitydinbthprimaryoand. secondary is4 determined by the; electrode surface and theaniram and thavolteais detelzmind by? :the length iaith@ fblumunfelectrolyte,,through- 'which the current'. must ,pass in eachhcell; .thecurrentdensity. and

voltage in each cell -being* regulatedat ,will

toy ymaintain the electroly tesv in molten y con- ,dtiomand to decomosethem. The current liberatesbarium an sodium. atthe surface of thelead in the primary cell, therebyA producing an ,alloy ofbarium-leadfsodium, which isthenonducted into or circulated through thel secondary chamber ,bv means of the centrifugal pump,-and soonbecomespractically homogeneous and Vof uniform temperature throughout theentire The current thenpasses from the surface of the alloy in thesecondary chamber (constituting the secondary anode) through the moltencyanid to the solid cathode; the liberated anions (CN) combining withbarium at the surface of the alloy to form barium cyanid, whichaccumulates in the electrolyte. The liberated anions (CN) may alsocombine with sodium at the surface of the alloy, `but this is of noconsequence since the electrolyte consists of molten sodium cyanid. V

The liberated anions cannot :combine with thei heavy'metal of the alloy,e. g., to form "a cyanid which would contaminate the sec-` ondaryelectrolyte or the product, and which would then yield, by electrolysis,lead at the solid cathode,-for reasons set forth in application 575,819;-none of4 the heavy metals combining with carbon and nitrogenl or.cyanogen to vform cyanids or cyanamids which are stable at thetemperature of the operation. This feature is of great importance inthis process.

Metallic sodium is liberatedat the cathode but as soon as an appreciableroportion of barium cyanid is present,whic may be purposely introducedat theve'ry start, the me-v tallic lsodium displaces the barium whichlatter then immediatelycombines with carbon, free or combined, to formamorphous barium carbid; and this substance remains suspendedyin thecyanid. Nitrogen may then be introduced through pipe 21 andwill pass'down through the hollow shank ofthe cathode 13 to the'lower surfacethereof, and there spread out in the form of a thin layer between theface of the cathode, or plunger, since it may be sol termed, and themolten alloy, and thus come into effective reactive Contact with thesuspended barium carbid with which it combines to produce barium cyanid.rll`he barium in the barium cyanid isv then displaced by the metallicsodium at the cathode, with the consequent production of sodium.cyanidland metallic barium which latter again becomes available for theproduction of more carbid. If there 4,is no free carbon present thebarium will seize upon one elementv` of combined carbon yin. the sodiumvcyanid to form sodium cyanamid which is'perfectly stable; but thislatter substance is vromptly reconverted v'into sodium cyanidJ assoon-.as free carbon is added. f Carbon in theform of' charcoal, fromwhich the'air and moisture-have been re'- moved by heat and vacuum maybe introduced through the hopper into the reactive chamber. Fuel oil maybe introduced through the oilfeed device under pressure,

and will thencome into contact with the and thence by electrolysis intothe secondary electrolyte', it becomes unnecessary to supply more,-forthe reason that the reactive metal is used over and over again, andtherefore no more barium chlorid need be added to the primaryelectrolyte, which may thereafter consist substantially' of sodiumchlorid. lf there is any loss, however, of available barium in thealloy, or ofvbarium carbid or kcyanid in the melt, through anyunavoidable or inadvertent circumstance or by being withdrawn in thefinished product, or for any other reason, the deficiency may besupplied from time to time by adding barium chlorid to the electrolytein the primary cell, or by supplying'it in any other manner.

The temperature of the lower end of the secondary cathode or plunger ifsubmerged in the red hot alloy would be, of course, substantially equalto that of the molten metal itself; but when the face of the plunger israised slightly above this eiiicient metallic heatconductor, Il nd thatsuicient heat may be conducted away through the shankv of the -plungerto the heavycopper conductors on the outside of the furnace to mit ' thecarbid, whereas if the ammonia is firstintroduced into the red hot alloyit is there partly decomposed into its elements, nitrogen (in the atomicstate) and hydrogen, but

th1s atomic nitrogen, unless instantly absorbed, passes into themolecular state, (N2). When molecular nitrogen rises into the moltencyanid it does not combine with the suspended -carbid with such avidity,as does the atomic nitrogen.' The absorption of' molecular nitrogen, inother words, is efvfected somewhat more slowly than the absorption ofatomic nitrogen. While it is disadvantageous for this reason to firstintroduce ammonia into the red hot alloy and then permit the nitrogen torise into thc cyanid, this objection does not hold with nitrogenobtained from the air,-z'. e., molecular nitrogen, which mayadvantageously be first introduced into the molten metal for the purposeof preheating it before it comes into contact with the carbid. Theauxiliary nitrogen pipe 21 may be used for this purose. p When thereaction vessel is suliciently full of cyanid it becomes necessary tovfinish or clarify the charge. The flow of gas should be stopped, andthe sodium liberated a short time longer in order to insure thedecomposition of all of the barium cyanid by sodium-which should be inexcess in the alloy-after which the suspended materials in the massshould be allowed to settle.

Barium carbid has a specific gravity somewhat greater than that ofmolten cyanid, and it, together with the excess carbon, will settle inthe course of time through the tranquil, undisturbed melt to the surfaceof the alloy after which the clear molten cyanid, or any part of it, maybe tapped off at one of the spouts above the surface of the alloy.Another method of finishing a charge of cyanid consists in limiting orwithdrawing the supply of sodium in the bath and in the alloy so thatall of the residual suspended carbon and carbid may be permanentlyconverted into barium cyanid, and the melt will consist of a clearmolten mixture of substantially pure sodium cyanid and barium cyanidwhich may be drawn oil" and utilized as such.

The respective proportions of the two cyanids may be controlled at will;but in general the sodium cyanid shouldbe greatly in excess.

It will be apparent from a consideration of the above reactions that afree reactive metal must be employed at some point in the cycle, or inlieu thereof a compound which will yielda free reactive metal at somepoint in the cycle, and that the use of any salt or compound which whenintroduced into the. molten mass or employed under any of the conditionsof the process will yieldsuch reactive metal, is within the scope of myinvention. It will be apparent, also, that a' carbid, nitrid, cyana mid,or cyanid of the reactive metal 1f of sufficient purity and in suitablephysical condition may be employed at the outset instead of the reactivemetal itself, and that this is possible by reason of the fact that theinitial carbid or nitrid, under the condi-` tions of the process, willbe converted into either cyanamid or cyanid of the reactive metal, andthat the alkali metal,-sodium or potassium will thereupon liberate-andset free the reactive metal-in metallic form. Other reactive metal saltsmay be similarly introduced and decomposed with consequent liberation ofa free reactive metal but the method is slightly objectionable for thereason that it introduces an impurity or diluent, e. g., sodium chloridinto the final cyanid. Thus barium chlorid, lithium chlorid, etc., ifintroduced into the molten cyanid will'melt and dissolve therein andcome into contact with the liberated sodium or potassium or thatcontained in the alloy, which will then decompose such chlorids with theformation of sodium or potassium chlorids, and metallic barium, ormetallic lithium will be liberated, according to the following equation:

(6) LiCl+Na=NaCl+Li (free metal).

Other reactive metals may be employed instead of barium,notably,lithium, strontium, and calcium, in which event the reactions will bequite similar to those indicated for barium.

The reactive metals chromium, titanium, vanadium, etc., will also bringabout the synthesis of sodium` cyanid under this process, although themechanism of the intermediate reactions is not the same inall cases,Aand the process is somewhat slower.

What I claim, is:

l. In a process of producing alkali-metalcyanogen compounds and thelike, th'e steps whlch comprise separatingr alkali-metal from a moltenmetallic bath and reacting on the separated metal with a nitrogen-carboncompound.

2. In a process of producing alkali-metalcyanogen compounds and thelike, the steps which consist in electrolytically separating manganese,cerium,

alkali-metal from a molten metallic bath and cyanogen compounds and thelike, the steps which consist in electrolytically depositing alkalimetal of the compound to be produced, and similarly depositing areactive metal,7 reacting on the reactive metal with carbonaceous andnitrogenous reagents to form a nitrogen-carbon compound of such metaland substituting the alkali-metal aforesaid for the reactive metal insaid compound.

5. ln a process of producing cyanogen compounds and the like. the stepswhich consist in effecting a reaction between electrolytically liberatedreactive metal and acarbonaceous reagent within a bath of fused mixedsalts and reacting on the compound so formed with a nitrogenous reagent.

6. ln a process of producing cyanogen compounds and the like the stepwhich comprises edecting a chemical reaction between a carbonaceousreagent and an electrolytically liberated metal within a. bath of fusedsalt to form an amorphous carbon compound of said metal.

7. In a process of producing cyanogen compounds and the like, the stepswhich comprise effecting a chemical reaction vbetween a carbonaceousreagent and an electrolytically liberated metal within a 'bath of fusedsalt to vform an amorphous carbon compound of said metal, and reactingon said carbon compound with a nitrogenous reagent.

8. ln a process of producing cyancgen compounds and the like, the stepswhich comprise effecting a chemical reaction between a carbonaceousreagent and an elec-A trolytically liberated metal to form an amorphouscarbon compound of said metal, and reacting on said carbon compound witha nitrogenous reagent to form a carbon-nitrogen compound of saidmetal,-the reactions taking place within a bath 'of fused salt.

9. In a process of producing cyanogen compounds and the like the stepswhich comprise electrolytically depositing a metal from a bath of fusedsalt and reacting on such metal with a carbonaceous reagent to form acarbon compound, said compound being held in suspension in the salt, andre acting on the suspended carbon compound with a nitrogenous reagent.

10. ln a process of producing cyanogen compounds and the like the stepswhich comprise electrolytically depositing a metal from a bath of mixedfused cyanogen compounds, the radical forming constituents of one atleast of which are the same as those of the compound to be produced, oneof said fused compounds including an alkaline metal and another a metalbelonging to a dierent group of metals, and reacting on such metal withcarbonaceousreagent.

11. lin a process of producing cyano en compounds and the like the stepswhich comprise electroytically depositing a metal from a bath of mixedfused alkali and alkaline earth cyanogen compounds, and react-` ingthereon in such bath with carbonaceous and nitrogenous reagents to forma nitrogen-carbon compound of the metal.

12. ln a process of producing a compound consisting of a metal and acombination of elements capable of forming a radical the steps whichconsist in electrolytically depositing a metal from a bath whichcomprises the said combination of elements and reacting on said metalwith a reagent to form a substance which is held in suspension in saidbath.

13. The process of producing alkali-metal cyanogen compounds and thelike, which includes liberating alkali-metal by passing a current ofelectricity through a fused bath from a substance which contains suchalkalimetal as one of the constituents thereof, forming acarbon-nitrogen compound in sail.-I bath and reacting on the liberatedalkalimetal with said compound.

14. The process of producing alkali-metal cyanogen compounds and thelike, which includes liberating an alkali-metal and a reactive metal bypassing a current of electricity through a fused bath from a body ofalloy which contains said metals, forming a carbon-nitrogen compound ofthe reactive metal in said bath and reacting on the liberatedalkali-metal with said compound.

15. In a process of producing cyanogen compounds and the like, the stepswhich consist in electrolytically liberating a reactive metal, reactingthereon with a molten carbonaceous reagent to form a carbid, at atemperature below that at which such carbid will fuse, and edecting areaction between said carbid and a nitrogenous reagent.

16.'The process of forming a carbonaiitrogen compound which compriseselectrolytically depositing a plurality of metals in the presence ofnitrogenous and carbonaceous reagents, one of said metals forming anitrogenrarbon compound with constituents of said reagents and anotherof said metals being thereafter substituted in said compound for thefirst.

17. The process of producing alkali-metal cyanogen compounds and thelike, which involves reacting with a carbonaceous reagent on freereactive-metal to form a carbon compound thereof, reacting on saidcompound with a nitrogenous reagent to form a carbon-nitrogen compound,electrolytically dissociating an alkali-metal from a mass of moltenalloy, and reacting onthe free alkali-metal with said carbon-nitrogencompound.

18.. The process of producing a carbonnitrogen compound which includesforming a carbon compound within a mass'of electrolyte through which anelectric current is owing, said electrolyte being in contact with afluid body of relatively high density which supplies at l'ea'st one ofthe ingredients of the compound aforesaid, and reacting on said compoundwith a nitrogenous reagent.

19. The process of roducin'g a carbonnitrogen compound which includesforming a carbon compound Within a mass of electrolyte through which anvelectric current is flowing said electrolyte being in contact with 1o afluid body of relatively high density which supplies at least one of'the ingredients of the compound aforesaid, and reacting on said compoundwhile in said electrolyte, with a nitrogenous reagent.

In witness whereof, I subscribe my signa- 15 ture, in the presence oftwo Witnesses.

CHARLES E.4 ACKER.

lVitnesses:

WALDo M. CHAPIN, WILLIAM C. LANG.

